CN111004105A - 一种(z)型7-碘-5-异丙基-6-烯-2-酮化合物、其制备方法及用途 - Google Patents

一种(z)型7-碘-5-异丙基-6-烯-2-酮化合物、其制备方法及用途 Download PDF

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CN111004105A
CN111004105A CN201911257877.8A CN201911257877A CN111004105A CN 111004105 A CN111004105 A CN 111004105A CN 201911257877 A CN201911257877 A CN 201911257877A CN 111004105 A CN111004105 A CN 111004105A
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雷声
刘志华
王凯
李振杰
王昆淼
蒋举兴
冒德寿
高莉
张翼鹏
者为
杨影
周强辉
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China Tobacco Yunnan Industrial Co Ltd
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Abstract

本发明公开了一种(Z)型7‑碘‑5‑异丙基‑6‑烯‑2‑酮化合物，其立体结构式为：

Description

一种(Z)型7-碘-5-异丙基-6-烯-2-酮化合物、其制备方法及 用途
技术领域
本发明属于有机合成技术领域，具体涉及一种(Z)型7-碘-5-异丙基-6-烯-2-酮、其制备方法及用于合成(Z)型茄酮的用途。
背景技术
茄酮是烟草中的一种非常重要的香味物质，对烟草吃味和香型有重要影响。茄酮能使烟香更加丰富饱满，改善口感，具有清新的红茶、清香、草香等香味，且有微甜香味。由于茄酮的加入任何烟丝中都显示出独特的效果，其除杂气、增香及增劲头、以及与烟丝的协调性等至今没有任何一个单体香料能与其匹敌。茄酮在烟叶中含量极微(仅为干重的0.0036％)，用提取的方法获取这类物质显然不具有应用价值。因此，只有通过人工合成的方法才能满足这种需求，但国内的纯的单体香料茄酮(考虑立体构型)的人工合成路线一直未能有突破性进展，现有人工合成方法有十几种，但纯的(Z)型茄酮单体还没有合成出来。茄酮产物的有四种立体构型控制(C5手性碳R、S构型和C6、C7双键的E、Z构型)，(Z)型茄酮单体为对消旋体(S,Z)-5-异丙基-8-甲基-6,8-二烯-2-酮和(R,Z)-5-异丙基-8-甲基-6,8-二烯-2-酮，纯的(Z)型茄酮单体合成的难点在于立体构型的控制上。为解决上述问题提出本发明。
发明内容
为了合成出立体构型不同的(Z)型茄酮单体，本发明首先合成出(Z)型中间体：即(S,Z)-7-碘-5-异丙基-6-烯-2-酮、或(R,Z)-7-碘-5-异丙基-6-烯-2-酮，然后用于(Z)型茄酮单体的合成。
本发明的技术方案如下：
本发明第一方面公开了一种(Z)型7-碘-5-异丙基-6-烯-2-酮，其特征在于，其立体结构式为：
Figure BDA0002310801350000021
其名称为：(S,Z)-7-碘-5-异丙基-6-烯-2-酮、或(R,Z)-7-碘-5-异丙基-6-烯-2-酮。
本发明第二方面公开了所述(Z)型7-碘-5-异丙基-6-烯-2-酮的制备方法，其特征在于，包括如下步骤：
①将原料异戊醛和甲基乙烯基酮在催化剂和共催化剂作用下，得到化合物(S)-2-异丙基-5-羰基己醛、或(R)-2-异丙基-5-羰基己醛；
②将步骤①得到的(S)-2-异丙基-5-羰基己醛、或(R)-2-异丙基-5-羰基己醛与碘甲基三苯基碘化膦进行反应，得到所述的(Z)型7-碘-5-异丙基-6-烯-2-酮，即：(S,Z)-7-碘-5-异丙基-6-烯-2-酮、或(R,Z)-7-碘-5-异丙基-6-烯-2-酮；
其反应式为：
Figure BDA0002310801350000022
优选地，步骤①所述催化剂为(S)-2-(甲氧基二苯甲基)吡咯烷、或(R)-2-(甲氧基二苯甲基)吡咯烷，所述共催化剂为3,4-二羟基苯甲酸乙酯；原料甲基乙烯基酮与异戊醛的摩尔比为(1﹕1.0)-(1﹕2.0)；2-(甲氧基二苯甲基)吡咯烷与异戊醛的摩尔比为(0.1﹕1.0)-(0.1﹕2.0)；3,4-二羟基苯甲酸乙酯与异戊醛的摩尔比为(0.2﹕1.0)-(0.2﹕2.0)；反应温度为-10℃-50℃，反应时间为20-30h。
优选地，步骤②的反应是在碱性溶剂条件下进行，并加入添加剂；所述溶剂为四氢呋喃，碱为六甲基二硅基胺基钠，所用添加剂为六甲基磷酰三胺；所述2-异丙基-5-羰基己醛与(2-甲基烯丙基)膦酸二乙酯的摩尔比为(1﹕1.0)-(1﹕1.5)；2-异丙基-5-羰基己醛与六甲基二硅基胺基钠的摩尔比为(1﹕1.0)-(1﹕1.5)；2-异丙基-5-羰基己醛与六甲基磷酰三胺的摩尔比为(1﹕4.0)-(1﹕5.0)；反应温度为-100℃-室温，反应时间为2-10h；所述室温为40℃；六甲基磷酰三胺是一个很好的非质子极性溶剂，可以增加碱性，明显提高反应活性。
本发明第三方面公开了所述(Z)型7-碘-5-异丙基-6-烯-2-酮用于制备(Z)型茄酮的用途。
优选地，制备(Z)型茄酮的步骤为：将(Z)型7-碘-5-异丙基-6-烯-2-酮与异丙烯基硼酸频哪醇酯在催化剂进行反应，即得到所述的(Z)型茄酮：(S,Z)-5-异丙基-8-甲基-6,8-二烯-2-酮或(R,Z)-5-异丙基-8-甲基-6,8-二烯-2-酮；其反应式为：
Figure BDA0002310801350000031
该反应是在碱性溶剂条件下进行；所述溶剂为四氢呋喃，碱为氢氧化钠；催化剂为[1,1'-双(二苯基膦基)二茂铁]二氯化钯；其中7-碘-5-异丙基-6-烯-2-酮与异丙烯基硼酸频哪醇酯的摩尔比为(1﹕1.0)-(1﹕2.0)；7-碘-5-异丙基-6-烯-2-酮与氢氧化钠的摩尔比为(1﹕1.5)-(1﹕2.5)；催化剂与7-碘-5-异丙基-6-烯-2-酮的摩尔比为(0.05﹕1.0)-(0.05﹕2.0)；反应温度为0℃-100℃，反应时间为2-10h。
本发明的有益效果：
1、本发明首次人工合成出用于茄酮单体制备的纯的(Z)型中间体：(S,Z)-7-碘-5-异丙基-6-烯-2-酮、或(R,Z)-7-碘-5-异丙基-6-烯-2-酮。
2、本发明的制备方法中加入了少量的六甲基磷酰三胺，六甲基磷酰三胺是一个很好的非质子极性溶剂，可以增加碱性，明显提高反应活性和产率。
3、本发明首先合成出(Z)型中间体(S,Z)-7-碘-5-异丙基-6-烯-2-酮、或(R,Z)-7-碘-5-异丙基-6-烯-2-酮，然后用于(Z)型茄酮的合成，首次得到纯的(Z)型茄酮：(S,Z)-5-异丙基-8-甲基-6,8-二烯-2-酮、或(R,Z)-5-异丙基-8-甲基-6,8-二烯-2-酮。合成步骤大幅缩短，安全性高；(Z)型茄酮产率可达到50％以上。
具体实施方式
下面通过实施例进一步阐述本发明，目的仅在于更好地理解本发明内容，而不是对本发明的限制。
实施例1：(S)-2-异丙基-5-羰基己醛、或(R)-2-异丙基-5-羰基己醛的合成
将73mg的(约0.4mmol)3,4-二羟基苯甲酸乙酯置于圆底烧瓶中，依次加入53.48mg的(0.2mmol)(S)-2-(甲氧基二苯甲基)吡咯烷，215μL的(约2mmol)异戊醛和243μL的(约3mmol)甲基乙烯基酮，反应在室温下搅拌，固体溶解，搅拌24小时。
反应结束后，旋转蒸发除去剩余的甲基乙烯基酮，剩余液体用石油醚﹕乙酸乙酯＝20﹕1的柱层析分离得到淡黄色液体230.1mg，产率为74％；分析为(S)-2-异丙基-5-羰基己醛即
Figure BDA0002310801350000041
分析如下：
1H NMR(400MHz,Chloroform-d)δ9.59((d,J＝2.8Hz,1H),2.47(m,1H),2.35(m,1H),2.11(s,3H),2.07-1.99(m,2H),1.85-1.70(m,2H),0.98(d,J＝6.6Hz,3H),0.95(d,J＝6.6Hz,3H)。13C NMR(101MHz,Chloroform-d)δ208.05,205.28,57.50,41.23,29.97,28.34,20.25,19.44,19.31。[α]+47.754°(589nm),(c 0.54g/100mL,CHCl3)。
将催化剂换成(R)-2-(甲氧基二苯甲基)吡咯烷，其他不变。产率也为74％；分析为(R)-2-异丙基-5-羰基己醛，即
Figure BDA0002310801350000042
分析如下：
1H NMR(400MHz,Chloroform-d)δ9.59(d,J＝2.8Hz,1H),2.47(m,1H),2.35(m,1H),2.11(s,3H),2.07-1.97(m,2H),1.86–1.69(m,2H),0.98(d,J＝6.6Hz,3H),0.95(d,J＝6.6Hz,3H)。13C NMR(101MHz,Chloroform-d)δ208.04,205.28,57.49,41.23,29.97,28.33,20.24,19.44,19.32。[α]-47.128°(589nm),(c 0.54g/100mL,CHCl3)。
实施例2：(Z)型中间体，即(S,Z)-7-碘-5-异丙基-6-烯-2-酮、或(R,Z)-7-碘-5-异丙基-6-烯-2-酮的合成
将1166mg的(约2.2mmol)碘甲基三苯基碘化膦置于反应瓶中，加入3mL的四氢呋喃，加入1.1mL浓度为2M的(约2.2mmol)六甲基二硅基胺基钠的四氢呋喃溶液，在室温下搅拌15分钟，体系变成亮红色。将体系冷却至零下78℃，加入1.6mL的(约9.2mmol)六甲基磷酰三胺，最后加入312mg的(约2mmol)实施例1得到的(S)-2-异丙基-5-羰基己醛在2mL四氢呋喃中的混合液。在零下78℃下搅拌4小时。
反应结束后，向体系中加入2mL饱和碳酸氢钠溶液，硅藻土过滤，滤液用乙酸乙酯萃取三次，合并有机相用无水硫酸钠干燥，浓缩，剩余液体用石油醚：乙酸乙酯＝30：1进行柱层析，得到淡黄色液体387mg，产率为69％。经分析为(S,Z)-7-碘-5-异丙基-6-烯-2-酮，即
Figure BDA0002310801350000051
分析为：
1H NMR(400MHz,Chloroform-d)δ6.31(d,J＝7.4Hz,1H),5.86(dd,J＝9.8,7.4Hz,1H),2.49–2.31(m,2H),2.24(m,1H),2.12(s,3H),1.82(m,1H),1.69(m,1H),1.50(m,1H),0.92(d,J＝6.8Hz,3H),0.88(d,J＝6.9Hz,3H)。13C NMR(101MHz,Chloroform-d)δ208.83,143.31,83.88,50.03,41.21,31.86,30.13,25.29,20.35,19.23。[α]+34.839°(589nm),(c0.62g/100mL,CHCl3)。
换成得到的R)-2-异丙基-5-羰基己醛，其他不变。得到淡黄色液体380mg，产率为68％。经分析为(R,Z)-7-碘-5-异丙基-6-烯-2-酮，即
Figure BDA0002310801350000052
分析为：
1H NMR(400MHz,Chloroform-d)δ6.31(d,J＝7.4Hz,1H),5.86(dd,J＝9.8,7.4Hz,1H),2.44–2.35(m,2H),2.24(m,1H),2.12(s,3H),1.82(m,1H),1.69(m,1H),1.50(m,1H),0.92(d,J＝6.8Hz,3H),0.88(d,J＝6.9Hz,3H)。13C NMR(101MHz,Chloroform-d)δ208.83,143.31,83.88,50.03,41.21,31.86,30.13,25.29,20.35,19.23。[α]-34.032°(589nm),(c0.62g/100mL,CHCl3)。
实施例3：(Z)型中间体即(S,Z)-7-碘-5-异丙基-6-烯-2-酮、或(R,Z)-7-碘-5-异丙基-6-烯-2-酮用于(Z)型茄酮单体的合成
将731mg的(约1mmol)[1,1'-双(二苯基膦基)二茂铁]二氯化钯置于反应管中，加入70mL的四氢呋喃；将2802mg(约10mmol)实施例2得到的(S,Z)-7-碘-5-异丙基-6-烯-2-酮、和2.8mL的(约15mmol)异丙烯基硼酸频哪醇酯混合在四氢呋喃中得到30mL混合溶液，将此30mL混合溶液加入到上述反应管中；最后加入2M的氢氧化钠水溶液10mL(约20mmol)于上述反应管中；在60℃下搅拌5小时。
反应结束后，向体系中加入水，用乙醚萃取三次，合并有机相用无水硫酸钠干燥，浓缩得到粗产品，粗产品用石油醚﹕乙酸乙酯＝30﹕1通过柱层析分离，得到淡黄色液体1425mg，产率为73％。经分析为(5S,6Z)型茄酮(S,Z)-5-异丙基-8-甲基-6,8-二烯-2-酮，即
Figure BDA0002310801350000061
分析如下：
1H NMR(400MHz,Chloroform-d)δ5.97(d,J＝12.0Hz,1H),5.09(t,J＝11.6Hz,1H),4.95–4.81(m,3H),2.45-2.43(m,1H),2.41-2.30(m,2H),2.10(s,3H),1.85(s,3H),1.81–1.77(m,1H),1.6-1.51(m,1H),1.37(m,1H),0.92-0.89(d,J＝6.8Hz,3H),0.89-0.86(d,J＝6.8Hz,3H)。13C NMR(101MHz,Chloroform-d)δ209.34,141.83,133.67,132.36,115.43,42.90,41.94,32.48,29.98,26.41,23.53,20.23,19.52。[α]+9.355°(589nm),(c0.62g/100mL,CHCl3)。
换成实施例2得到的(R,Z)-7-碘-5-异丙基-6-烯-2-酮，其他不变。得到淡黄色液体1345mg，产率为69％。经分析为(5R,6Z)型茄酮(R,Z)-5-异丙基-8-甲基-6,8-二烯-2-酮，即
Figure BDA0002310801350000062
分析如下：
1H NMR(400MHz,Chloroform-d)δ5.97(d,J＝12.0Hz,1H),5.09(t,J＝11.6Hz,1H),4.87(m,3H),2.50-2.43(m,1H),2.42-2.32(m,2H),2.11(s,3H),1.85(s,3H),1.82-1.75(m,1H),1.56(m,1H),1.37(m,1H),0.90(d,J＝6.8Hz,3H),0.87(d,J＝6.9Hz,3H)。13CNMR(101MHz,Chloroform-d)δ209.34,141.83,133.67,132.36,115.42,42.90,41.94,32.47,29.97,26.40,23.53,20.23,19.52。[α]-9.839°(589nm),(c 0.62g/100mL,CHCl3)。
实施例4：(Z)型茄酮在卷烟烟丝加香中的应用
以某云产品牌样品卷烟为实验对象，根据烟丝重量计算香料添加量，将本发明合成的两种纯的(Z)型茄酮：(S,Z)-5-异丙基-8-甲基-6,8-二烯-2-酮(注射加香烟支为样品1)和(R,Z)-5-异丙基-8-甲基-6,8-二烯-2-酮(注射加香烟支为样品2)配成一定浓度的乙醇溶液，用CIJECTOR香精香料注射机，按照香料占烟丝重量百分比0.005％将其乙醇溶液均匀注射到烟支中；以同等条件下注射同样体积乙醇的烟支(样品0)为对照样，在相对湿度60％，22℃条件下平衡48小时，按照烟草行业标准《烟草在制品感官评价方法》(YC/T 415-2011)对三个样品进行感官对比评价，评价结果见下表。
Figure BDA0002310801350000071
备注：9分制评分法
从感官评价结果可以看出，相比于对照样，添加了(Z)型茄酮的两个样品带来明显的成熟烟香、干草香、清甜香等特征香气，与烟草本香的协调性好，烟香的丰富性、优雅度、烟气饱满度都得到提升，烟气的光滑细腻程度明显改善，还能掩盖杂气、改善余味。比较两个异构体香料的加香效果，(S,Z)-型茄酮主要在香气质、饱满度和烟气形态上提升作用明显；(R,Z)-型茄酮则主要在烟香丰富性、烟气细腻优雅度、余味回甜舒适度上提升较为显著。总体来看，两个(Z)型茄酮对卷烟烟香的丰富性、饱满度、香气质、烟气细腻优雅程度、降低杂气等方面有提升效果，两个异构体作用大体相似，侧重点略有不同，在卷烟香精香料的配方调香中具有很高的使用价值。

Claims (6)

1.一种(Z)型7-碘-5-异丙基-6-烯-2-酮化合物，其特征在于，其立体结构式为：
Figure FDA0002310801340000011
其名称为：(S,Z)-7-碘-5-异丙基-6-烯-2-酮、或(R,Z)-7-碘-5-异丙基-6-烯-2-酮。
2.一种根据权利要求1所述(Z)型7-碘-5-异丙基-6-烯-2-酮化合物的制备方法，其特征在于，包括如下步骤：
①将原料异戊醛和甲基乙烯基酮在催化剂和共催化剂作用下，得到化合物(S)-2-异丙基-5-羰基己醛、或(R)-2-异丙基-5-羰基己醛；
②将步骤①得到的(S)-2-异丙基-5-羰基己醛、或(R)-2-异丙基-5-羰基己醛与碘甲基三苯基碘化膦进行反应，得到所述的(Z)型7-碘-5-异丙基-6-烯-2-酮，即：(S,Z)-7-碘-5-异丙基-6-烯-2-酮、或(R,Z)-7-碘-5-异丙基-6-烯-2-酮；
其反应式为：
Figure FDA0002310801340000012
3.根据权利要求2所述的制备方法，其特征在于，步骤①所述催化剂为(S)-2-(甲氧基二苯甲基)吡咯烷、或(R)-2-(甲氧基二苯甲基)吡咯烷，所述共催化剂为3,4-二羟基苯甲酸乙酯；原料甲基乙烯基酮与异戊醛的摩尔比为(1﹕1.0)-(1﹕2.0)；2-(甲氧基二苯甲基)吡咯烷与异戊醛的摩尔比为(0.1﹕1.0)-(0.1﹕2.0)；3,4-二羟基苯甲酸乙酯与异戊醛的摩尔比为(0.2﹕1.0)-(0.2﹕2.0)；反应温度为-10℃-50℃，反应时间为20-30h。
4.根据权利要求2所述的制备方法，其特征在于，步骤②的反应是在碱性溶剂条件下进行，并加入添加剂；所述溶剂为四氢呋喃，碱为六甲基二硅基胺基钠，所用添加剂为六甲基磷酰三胺；所述2-异丙基-5-羰基己醛与(2-甲基烯丙基)膦酸二乙酯的摩尔比为(1﹕1.0)-(1﹕1.5)；2-异丙基-5-羰基己醛与六甲基二硅基胺基钠的摩尔比为(1﹕1.0)-(1﹕1.5)；2-异丙基-5-羰基己醛与六甲基磷酰三胺的摩尔比为(1﹕4.0)-(1﹕5.0)；反应温度为-100℃-室温，反应时间为2-10h；所述室温为40℃。
5.根据权利要求1所述(Z)型7-碘-5-异丙基-6-烯-2-酮用于制备(Z)型茄酮的用途。
6.根据权利要求5所述的用途，其特征在于，制备(Z)型茄酮的步骤为：将(Z)型7-碘-5-异丙基-6-烯-2-酮与异丙烯基硼酸频哪醇酯在催化剂[1,1'-双(二苯基膦基)二茂铁]二氯化钯作用下进行反应，即得到所述的(Z)型茄酮：(S,Z)-5-异丙基-8-甲基-6,8-二烯-2-酮或(R,Z)-5-异丙基-8-甲基-6,8-二烯-2-酮；其反应式为：
Figure FDA0002310801340000021
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